New brighteners,compositions thereof and processes for using same

ABSTRACT

A BRIGHTENER COMPOSITION PARTICULARLY ADAPTED FOR THE BRIGHTENING OF POLYESTERS COMPRISING (A) A COMPOUND OF THE FORMULA:   2-((PHENYL)-CH=CH-(1,4-PHENYLENE)-)-   2H-ANTHRO(2,3-D)TRIAZOLE   AND (B) A NON-IONIC SURFACTANT. WHEN SUCH A COMPOSITION IS EMPLOYED FOR BRIGHTENING OF A POLYESTER-COTTON BLEND, SUCH COMPOSITION MAY ADDITIONALLY CONTAIN A STILBENECYANURIC BRIGHTENER. THE ACTIVE BRIGHTENER IS PRECIPITATED BY DROWNING THE ABOVE COMPOSITION, EITHER ALONE OR TOGETHER WITH A SUITABLE DETERGENT IN THE WASH WATER.

United States Patent U.S. Cl. 252-452 14 Claims ABSTRACT OF THEDISCLOSURE A brightener composition particularly adapted for thebrightening of polyesters comprising (a) a compound of the formula:

and (b) a non-ionic surfactant. When such a composition is employed forbrightening of a polyester-cotton blend, such composition mayadditionally contain a stilbenecyanuric brightener. The activebrightener is precipitated by drowning the above composition, eitheralone or together with a suitable detergent in the wash water.

This application is a continuation-in-part of U.S. application Ser. No.539,283, filed Apr. 1, 1966, now abandoned.

The present invention is directed to certain novel brighteningcompositions containing a stilbene naphthotrazole brightener,particularly effective in the brightening of polyester materials; moreparticularly, the present invention is directed to such a novelbrightening composition comprising a stilbene naphthotriazole brightenerin a nonionic surfactant, such composition when drowned in water beingeifective to brighten polyester textiles.

It is well known that textiles tend to develop a yellowish shade onaging which cannot be removed by ordinary methods of bleaching orWashing. The heretofore used methods of bluing white material with bluepigments or fugitive blue dyestuffs have become quite obsolete in modernlaundry practice and have been largely superseded by methods employingfluorescent optical bleaching agents or brighteners as additives to thesoap or detergent in the washing bath. These brightening agents areusually conveniently supplied commercially in the form of intimateadmixtures with the soap or detergent in bars, flakes, powders, etc. Thefluorescent optical bleaching agents perform their desired function byvirtue of their characteristic absorption of ultra-radiation andsubsequent conversion of this energy to light energy within the visiblespectrum. This converted and emitted light energy tends to neutralizeany yellowness of the material and thereby increase the apparentwhiteness thereof.

Compounds which have been suggested and employed as fluorescentbrightening agents include the following:

(I) Acylated derivatives of 4,4-diamino-stilbene-2,2-

disulfonic acid.

(II) Acylated derivatives of 4,4-diamino-diphenyl-2,2-

disulfonic acid.

(III) Triazyl derivatives of diamino stilbene disulfonic acid.

ice

(IV) Triazyl derivatives of diamino diphenyl disulfonic acid.

(V) Acylated derivatives of diamino dibenzothiopheue dioxide, etc.

(VI) Stil'bene-cyanuric compounds.

Compounds of the Types I and II are disclosed in U.S. Pats. 2,518,059and 2,643,198, and in British Pat. 584,484.

Compounds of the Types III and IV are disclosed in U.S. Pat. 2,618,636and in application Ser. No. 381,856 published May 11, 1954 by the A.P.C.

Compounds of Type V are exemplified in U.S. Pats. 2,563,493 and2,563,795.

Compounds of Type VI are exemplified in U.S. Pats. 2,526,668, 2,539,766,2,694,064, 2,875,106, 2,473,475, 2,595,030, 2,612,501, 2,618,636,2,658,064, 2,658,065, 2,660,578, 2,666,052, 2,667,458, 2,703,801,2,742,43 4, 2,745,830, 2,840,557, 3,018,287, 3,127,270, 3,132,106, and3,177,207.

In addition to the five types mentioned above, other triazyl compoundshave been suggested. Thus, U.S. Pat. 2,713,054 discloses monotriazolesof the type:

l CH3 U.S. Pat. 2,713,055 discloses monotriazoles of the type:

NaOaS SOaNa U.S. Pat. 2,713,056 discloses monotriazoles of the type:

wherein X designates oxygen, sulfur, or imino, and Y alkyl or aryl.

U.S. Pat. 2,713,057 discloses monotriazoles containing a stilbene moietyof the type formulated in claim 2:

None of the aforementioned patents relates to stilbene monotriazolescontaining a naphtho substituent. Such compounds, however, are disclosedin Pat. 2,784,183, and

representative of the compounds in the latter patent is the followingcompound:

N l N S 0311 Again, US. Pat. 2,784,184 relates to stilbene naphthornonotriazoles and bis-triazoles which, however, are devoid of watersolubilizing groups and contain vicinal to the ethylene bridge of thestilbene moiety or para thereto at least one sulfonyl or substitutedsulfonyl radical of It has now been discovered that a specific stilbenenaphthomonotriazole is an outstanding brightening agent for hydrophobicfibers, i.e., so-called fine fabrics," and particularly for Dacron(polyester) and nylon, especially where these fibers are laundered inconjunction with cellulosic materials, e.g., cotton.

Thus, it has been discovered in accordance with the present inventionthat a compound of the formula:

is particularly effective as a brightener for hydrophobic fibers,particularly, polyesters and polyamides. In this regard, it has beendiscovered in accordance with the present invention that when such abrightener is dissolved in a non-ionic surfactant and drowned in waterthe active brightener precipitates in an active form particularlyeffective for the brightening of such fine fabrics.

Moreover, it has been found in accordance with the present inventionthat a particularly effective composition for the brightening of mixedhydrophobic fibers and cotton can be provided through the employment ofa composition containing the aforementioned brightener dissolved in anon-ionic surfactant, such composition also containing astilbene-cyanuric brightener of Type VI set forth above.

It is therefore a principal object of the present invention to providenovel fine fabric brightener compositions, particularly adapted for thebrightening of polyester and polyamide materials alone or in combinationwith cotton.

It is yet a further object of the present invention to provide suchnovel brightener compositions comprising2-(4-styrylphenyl)-2H-naphthotriazole dissolved in a nonionicsurfactant, the active brightener being precipitated when suchcomposition is drowned in water.

It is yet a further object of the present invention to provide such anovel brightener composition wherein such composition additionallycontains a stilbene-cyanuric brightener capable of brightening thecotton portion of a mixed cotton-hydrophobic fiber blend.

Still further objects and advantages of the novel compositions of thepresent invention will become more apparent from the following moredetailed description thereof.

The above objects and advantages of the present invention are achievedthrough a brightening composition comprising a specifically identified2-(4-styrylphenyl)-2H- naphthotriazole brightener dissolved in anon-ionic sur- 1 factant. In accordance with the present invention, whensuch a brightener composition is drowned in water the active brighteneris precipitated, such brightener being eminently suitable for thebrightening of hydrophobic fibers, particularly polyesters. In thisregard, as will be illustrated hereinafter, it is an essential featureof the present invention that the brightener be dissolved in a non-ionicsurfactant since it is only through such combination of components thatthe outstanding brightening characteristics of the present invention canbe achieved.

In addition, since hydrophobic fibers, particularly polyesters areconventionally blended with cotton fibers, an additional embodiment ofthe present invention includes within the above-noted composition acyanuric cotton brightener. In this way, when such a composition isdrowned in Water, the precipitated active brighteners can suitablybrighten both the hydrophobic portion, i.e., polyester, and cottonportion of a suitable blended fabric.

As a still further embodiment of the present invention, such abrightener composition comprising the2-(4-styrylphenyl)-2H-naphthotriazole dissolved in a non-ionicsurfactant with or without an additional cyanuric brightener can beincluded within a conventional detergent composition. In this regard,such detergent can comprise any of the suitable anionic, cationic,non-ionic or amphoteric detergents conventionally employed in thelaundering art. It is only essential in accordance with the presentinvention, however, that a non-ionic surfactant be present so as todissolve the 2-(4-styrylphenyl)-2H-naphthotriazole brightener so as toallow precipitation when the composition is subsequently drowned inwater during the washing and brightening operation.

Thus, it has now been discovered in accordance with the presentinvention that a brightener of the formula:

has the outstanding ability when combined with a nonionic surfactant toprovide exceptional brightening results particularly when employed tobrighten a hydrophobic fabric, particularly, polyesters and polyamides,i.e., Dacron and nylon, and polyester fabrics in particular. In thisregard, as set forth above, such brightener has, unlike most opticalbrightening agents which preferentially brighten cotton or othercellulosic fibers when the same are present, the unique characteristicof preferentially brightening hydrophobic fibers such as Dacron andnylon, and thus being able to advantageously brighten Dacron, nylon andsimilar hydrophobic fibers even when mixed with cotton or othercellulosic fibers, either in a blended fabric or in a mixed laundry loadof cotton fabrics and fine fabrics. Thus, with the novel compositions ofthe present invention which contain in addition to the abovenotedbrightener and non-ionic surfactant a stilbenecyanuric type brightenerof Type VI set forth above, instead of the two brighteners acting toadversely effect each others performance, there is instead some uniquesynergistic action between the two resulting in the brightening of notonly cellulosic fibers, but also any Dacron and1 nylon fibers to whichthey may be applied simultan ous y.

The combination of the brightener of this invention with a cellulosicbrightener and particularly one of the sulfonated stilbene-cyanuric TypeV1 is unique in that brightening of both Dacron and nylon along withbrightening of cellulose is achieved notwithstanding the fact that thebrightener of this invention tends to cause the development of ayellowish cast on cellulose in the absence of the cellulose brightener,particularly in concentrations which are conventional for cellulosicbrighteners (i.e., 0.1 to 0.4% by weight based on the weight of thedetergent used).

The hydrophobic fiber brightener of the present invention is prepared bydiazotizing 4-amino stilbene and coupling it to 2-naphthylarnine andthereafter oxidizing the resultant product to produce the desiredtriazole.

The 4-amino stilbene is a known compound (see B55: 1239) and has amelting point of 151 C. The compound is prepared from 4-nitro stilbenewhich is also a known compound with a reported melting point of 157 C.(B55: 1239). Specific details as to the preparation of compound Aillustrating a preferred embodiment of the preparation thereof are givenbelow.

While the brightener of the present invention may be employed in avariety of ways to effect brightening of fine fabrics, e.g., polyestersin particular, particularly advantageous results are achieved when thebrightener is dissolved in a non-ionic surfactant and thereafter drownedin water during a conventional washing operation. Preferably, thebrightener of the present invention is dissolved in from about 5 to 500times its weight of a non-ionic surfactant having the molecularconfiguration of a condensation product of a reactive-hydrogenhydrophobe with from about 5 to about 30 moles of an alkylene oxide,preferably ethylene oxide, although propylene oxide, a butylene oxide,or mixtures thereof with ethylene oxide may be used. Suchreactive-hydrogen hydrophobic compounds are well known in the detergentart and comprise alcohols, phenols, and less importantly, amides,sulfonamides, amines, and carboxylic acids all having at least 5 carbonatoms in the hydrophobe moiety and preferably, from to 35 carbon atomstherein.

Such non-ionic surface active agents are well known in the art and maybe represented by the following general formula:

OHR-CHR R wherein R represents the residue of a hydrophobic organiccompound containing a reactive hydrogen and R represents hydrogen,methyl or ethyl, with the proviso that the total number of carbon atomsin the R groups should not be higher than 2, and x represents an integerof from 3 to 150, usually from 6 to 50. Numerous specific non-ionicsurfactants of this type, which may be used in the compositions of thepresent invention, are known in the art and include the polyalkyleneoxide condensates of aliphatic and aromatic organic hydroxy compounds,carboxy compounds and amino compounds described in US. Pat. 1,970,578,of alkyl phenols described in US. Pat. 2,213,477, of carboxylic acidamines described in US. Pat. 2,085,706, and of sulfonamides described inUS. Pat. 2,002,613, the disclosure of which are incorporated herein byreference. Typical examples of the alkylated phenols are:

isobutyl phenol n-butyl phenol diisobutyl phenol isoamyl phenol n-hexylphenol isooctyl phenol n-octyl phenol di-n-octyl phenol di-isopropylphenol nonyl phenol dinonyl phenol decyl phenol dodecyl phenoldi-dodecyl phenol hexadecyl phenol tri-octyl phenol tri-nonyl phenol Inthe above described amides, sulfonamides, mercapto compounds and amines,R can be similar to R for alcohols and additionally, R may be an arylmoiety containing preferably at least about 8 carbon atoms, and mostpreferably, at least about 10 carbon atoms, and illustrative of thesemoieties mention may be made of alkylated phenyl such as isobutylphenyl, diisobutyl phenyl, nonyl phenyl, dinonyl phenyl and the like.

Again, in accordance with the present invention, the novel brightener isdissolved in the non-ionic surface active compound in an amount suchthat the surface active compound is present in an amount of about 5 to500 times the weight of the brightener. Preferably, an amount of surfaceactive compound of from about 10 to about 300 times the weight of thebrightener is advantageously utilized in accordance with the novelbrightener compositions of the present invention.

As indicated above, when brightening a mixed hydrophobicfiber-cellulosic blend it is often desirable to include within thebrightener composition a cyanuric brightener of Type VI previously setforth. The cyanuric brighteners Type VI which are eminently suited foruse in accordance with the present invention for the brightening ofmixed fibers may be represented by the following general formula (in thefree acid form) wherein Y is sulfo or carboxy; wherein X and X areindependently (1) hydrogen, (2) halogen, (3) alkyl, (4) hydroxy, (S)hydroxyalkyl, (6) primary alkylamino, (7) secondary alkylamino, (8)hydroxyalkylamino, (9) arylamino, (10) oxyphenyl, (11) oxyalkyl, (12)morpholino and the mono and di-sulfo derivatives of (6), (7), (9), (10),(11) and (12). It is preferred that at least one of X and X is otherthan hydrogen, halogen, and hydroxy and Y be sulfo.

Specific cyanuric brighteners as illustrative of the above include:

Generally, the cotton brightener is employed in a Weight ratio to thehydrophobic texile brightener of from 1:1 to 100:1, preferably in aweight ratio of :1 to 30: 1.

As previously indicated, it is often suitable to incorporate thebrightener composition of brightener and nonionic surfactant in asuitable detergent composition so as to provide combined detergency andbrightening characteristics. Thus, the non-ionic surfactant solution ofbrightener may be blended with a detergent formulation in any one ofseveral ways.

Where the detergent in the laundering formulation is non-ionic, asolution of the brightener in the said nonionic is prepared within theconcentration limits of about 0.2 to and preferably at a concentrationof from 0.5 to 1%. This solution is then blended with an aliquot portionof the laundry detergent formulation (i.e., nonionic surfactant,builders, and other additives such as silicates, carboxymethylcellulose,etc.) to produce a paste. The paste is then further blended with theremaining portion of detergent formulation to give the desiredbrightener concentration therein which may vary from about 0.005% toabout 0.5% by weight based on the total composition.

Where the detergent in the laundering formulation is anionic, a solutionof the brightener in the non-ionic surface active agent is prepared butin more concentrated form (it is preferred to make a 5 %-10% solution)and add same to the anionic material. The preferred stage of addition iswhere the anionic is in the form of a 50-80% aqueous gel and preferablyat an elevated temperature, e.g., C. The brightener solution is blendedwith the anionic solution in this form and this blend is added to theremaining solids, i.e., builders, fillers, etc. of the finalformulation, after which spray drying results in the production of thebrightened built anionic detergent composition.

In such detergent compositions which are to be used for all purposelaundry-brightening properties (i.e., including cellulosic textiles) theconcentration of the cellulosic brightener may vary from about 0.05% toabout 0.5% by weight based on the weight of the detergent. As withrespect to the previous defined range limitations, however, it should beapparent that slightly lesser or greater amounts of the cellulosicbrightener can be employed where desired for particular purposes.

The detergents which are suitable include the general classes of anionicand non-ionic types, and as usually formulated, they contain a majoramount of inorganic builder salts (including alkaline salts) as fillersand detergency improvers. The most common alkaline builders are thephosphates, carbonates, borates and silicates. Typical phosphatesinclude sodium tripolyphosphate, tetra potassium pyrophosphate,tetrasodium pyrophosphate, potassium tripolyphosphate and the like.Other additives which are conventionally used include anti-redepositionagents, soil suspending agents, and the like,

A typical detergent formulation may be represented by the following:

Ingredient: Parts by weight Detergent 15-40 Sodium tripolyphosphate20-50 Sodium carbonate 20-50 Sodium sulfate 10-50 Sodium carboxy methylcellulose 0.5-2 Sodium metasilicate 5-15 The detergent may be any of thenon-ionic compounds described above and as examples of anionics, mentionmay be made of the following which have the indicated general structuresin the free acid form:

(1) Alcohol sulfates (RCH OSO H wherein R is an aliphatic chain,preferably alkyl of 12 to 22 carbons) e.g., sodium lauryl sulfate.

(2) Alkyl aryl sulfonates A1S 03B wherein Ar is benzene or naphthaleneand the Rs represent hydrogen or alkyl with about at least 6 carbons asalkyl substituents) e.g., sodium dodecyl benzene sulfonate.

(3) Alkyl sulfonates [RCH SO H wherein R is as in (1)] e.g., sodiumlauryl sulfonate.

(4) Sulfonated amides l-r (BOON-CH2CH2S 03H wherein R is as in (1) and Ris lower alkyl such as methyl, ethyl or cycloalkyl such as cyclopentylor cyclohexyl) e.g., sodium-N-methyl-N-lauroyl taurate.

Sulfonated esters (RCOOCH CH SO H wherein R is as in (1)) e.g., oleicacid ester of sodium isethionate (6) Sulfonated amines (RNHSO H whereinR is as in (7) Anionic analogs of polyoxyalkylated phenols (RQMROM-ilhos 03H wherein R represents an alkyl or plurality of alkyl substituents,R is alkylene of 2 to 4 carbons and n is the number of moles of alkyleneoxide (or equivalent) reacted and condensed with the phenolic hydroxy)e.g.

sodium salt of sulfated isooctylphenoxy nonaethyleneoxy ethanol.

Further examples and more details as to operable detergent compositionsincluding the types of non-ionic surface active materials, anionicsurface active materials and various additives including the inorganicbuilders may be found in the following US. patents:

(A) 2,941,951 which discloses numerous (1) non-ionic and anionicsurfactants, (2) detersive and foam improvers such as the alkali metalphosphates, borates, carbonates, sulfates, chlorides, silicates, higheraliphatic alcohols, higher fatty acid amides and alkylolamides, e.g.,lauroyl amide, lauroyl monoand di-alkylamides, lauroyl ethanolamide, andlauroyl diethanolamide,

(B) 2,965,678polyoxyethylene ethers of branched chain alcohols,

(B) 3,033,889phosphate ester of branched chain alcohols,

(D) 3,122,508phosphate ester surfactants and nonionic precursors thereofand numerous conventional additives,

(E) 3,168,478anionic phosphate surfactants, additives for detergentcompositions including soil suspending agents, perfumes, deodorants,disinfectants, corrosion inhibitors, sequestrants, foam stabilizers,hydratropes, etc. and non-ionic precursors for the anionic compounds.The preferred non-ionic surfactants are the alkyl phenolethylene oxidecondensates (see US. Pat. 2,941,951, column 4, lines 6-47).

The disclosures of the aforementioned US. patents are herebyincorporated by reference thereto as illustrating detergent compositionswhich are operable in the present invention.

As indicated above, the objects and advantages of the present inventionare achieved through a novel brightener composition which comprises 2 (4styrylphenyl) 2H- naphthotriazole dissolved in a non-ionic surfactant.In addition, in accordance with further embodiments of the presentinvention the novel brightener composition of the present invention cancontain a suitable cotton brightener, particularly of thestilbene-cyanuric type, and such brightener composition with or withoutthe cotton brightener may be included within a built detergentcomposition. In such composition, the detergent is preferably of thenon-ionic or anionic type.

While the use of the novel brightener composition of the presentinvention has been emphasized in combination with detergent compositionsfor laundering fine fabrics, it is, of course, clear that the brightenermay be used in other conventional ways to effect a brightening of thegeneral class of hydrophobic synthetic polymers of the polyester,polyarnide, polyurethane, polyolefin, vinyl polymer types. Suchtechniques include particularly the melt incorporation of the brightenerinto the polymer prior to final shaping (i.e., molding, extruding, fiberforming, film forming, etc.).

The novel composition of the present invention and the advantagesassociated therewith will now be illustrated by reference to thefollowing specific examples.

EXAMPLE 1 Preparation of hydrophobic textile brightener A:

At 40 C. a solution is prepared of 141.3 g. of 4-aminostilbene (0.725mol: molecular weight 195) in 665 cc. of glacial acetic acid. Thissolution is then added gradually with stirring to a mixture of:

2000 cc. water 185 cc. hydrochloric acid (38% CF.)

The mixture is then stirred and cooled in an ice bath at 2 C. and whilemaintaining the temperature at from 2 to 5 C., there is added gradually136.5 cc. of a sodium nitrite solution which contains 0.76 mol of sodiumnitrite on a 100% basis. The resultant diazonium reaction product isthen stirred for /2 hour at 05 C. in the presence of the slight excessof nitrite present therein. Thisexcess nitrite is then destroyed byadding just in excess of the stoichiometric amount of sulfamic acidrequired for this purpose.

There is then separately prepared a coupler solution by dissolving 115g. of 2-naphthylamine (0.796 mol) in 333 cc. of glacial acetic acid.This coupler solution is then slowly added to the diazonium reactionproduct described above. The mixture is then set for 2 hours at 0-5 0,after which 200 g. of sodium acetate crystals are gradually sprinkledinto the mixture. Stirring of the mixture is then continued for about 12hours at 0-5 C. until there is obtained a negative test for diazopresence (spot coupling with H acid on paper). The resultant reactionmixture contains the final reaction product as a slurry in the aqueousmedium and this slurry is filtered and the filter cake is then washedwith 4000 cc. of Water. The resultant dye cake is then dried in air atC. The yield of product is 272 g. (107% of theoretical yield).

The dye produced above is then oxidized to the final brightener by thefollowing procedure. Into a 3-liter 3-necked flask equipped with astirrer, thermometer, reflux condenser and heating mantle there arecharged:

136 g. of the dye produced above (0.35 mol) 1630 cc. picoline Thismixture is stirred for a half hour at room temperature at 27 C. whilethere are added:

226.5 g. of copper sulfate penta hydrate.

This amount of the copper sulfate corresponds to 0.907 mol of copper.The mixture is then heated for 2 hours at 100 C. and permitted to cooldown to 80-85 C. at which temperature there is added gradually to themixture 131 g. of sodium sulfide (100% basis) to give a slight excess ofsulfide (indicated by spot testing on paper with lead acetate solution).The charge is then further heated at 100 C. and clarified by filteringthrough a Celite filter. The filter cake which is copper sulfide iswashed with 400 cc. with picoline (at C.). The mother liquor and washliquor are then combined and cooled to 10 C. This cooling results in theformation of a copious precipitate which is filtered and the solid cakeon the filter is washed with 200 cc. of methanol, then with 2000 cc. ofwater and finally air dried at 80 C. The resultant yield is 99.7 g.which is 82% of theory.

As pointed out above, the 4-amino stilbene starting material is a knowncompound but a particularly outstanding procedure for producing thiscompound is as follows:

Into a 1-liter 3-necked round bottom flask equipped with stirrer,thermometer, reflux condenser, and. thermostatically controlled waterbath there are charged the following:

137 g. 4-nitrot0luene (molecular Weight 137) 127.2 g. benzaldehyde (1.2mols) 150 cc. Carbowax 400 (polyethylene glycol, molecular weight about400) 20 g. sodium N-methyl-p-toluene sulfonamide (0.097

mol) and 28 g. potassium carbonate, anhydrous (0.2 mol).

Percent by Weight Sodium dodecyl benzene sulfonate 15 Sodiumtripolyphosphate 2O Tetrasodium pyrophosphate Sodium sulfate Sodiumcarbonate 3 Sodium carboxyrnethyl cellulose 1 Sodium metasilicate 5 2.4ml. of the brightener solution which is prepared above The reactionmixture is stirred for hours at 60 C. 10 and which cfmtzllins g' z fif 5t after which time there is mixed with the charge 2000 cc. S t 1S a so amm ypoc cute 0 glve of Water at The Water layer is separated by .02 ofavailable chlorine 1n the bath. A 4.5 g. swatch decantation and theresidue is re-slurried in 2000 cc. of 9 cfitton andba g a Swatch ofDacmn are lmn3ersed 50 C. water. After settling, the water layer isagain 15 m t i at an agitate: therem for 9 minutes decanted and theresidue mixed with 1000 cc. of methanol 12 They are 4 tar y mused andand the mixture is then heated to C. After reaching dned' The Dacmn hasa brightness readmg of this temperature, the methanolic solution iscooled down EXAMPLE 3 to 0 C. and the resultant precipitate is filteredand x washed with 200 cc. of methanol. The solid is then 20 Examp 1e 21s iepeated usmg mpkice bnghtelier d d t C Th ildi C nd A, an equalwelght of a commercial brlghtener Wl'llCl'l i i Oven T 3, C a isa,{3-[N-methyl benzoxazolyl-(Z)]-ethylene. The bright Pro as a me Hg Pomo ness of the Dacron in this procedure is only 12.

EXAMPLE 2 The outstanding bringtening effect of the brightener 25 MPLE 4of this invention is illustrated on a Dacron textile ma- E ample 2 isagain repeated using in place of brightterial as follows. 0.1 g. of thebrightener produced in ener A, an equal weight of the commercial styrylnaphtho- EXample 1 is dlssolved n 0 cc. Of nonyl phenoxy nona oxazolebrightener. The brightness of the Dacron here ethyleneoxy ethanol (aliquid non-ionic surface active i 24, agent produced by the condensationon nonyl phenol 30 EXAMPLE 5 with 10 mols of ethylene oxide). Theresultant solution is then diluted to 1 liter with water. To cc. ofwater Example 2 is still once more repeated using in place there areadded 0.4 g. of a commercial detergent formuof brightener A, an equalweight of the following brightlation which comprises as the mainingredient: eners:

Compound Brightness (1)-.- N\ 20 N- -CH=OH 502011 U N Q Q l N 01 EXAMPLE6 Example 2 is again repeated except that the hypochlorite iseliminated. Similar excellent results are obtained.

EXAMPLE 7 Examples 3 and 4 are repeated eliminating the hypochlorite. Noimprovement in brightness is noted.

EXAMPLE 8 Example 2 is again repeated except that 0.008 g. of brightenerA is prepared in a solution of 100 ml. of dimethyl formamide and a 2 ml.aliquot of this solution is added to the hypochlorite-detergent bath.The brightness of the Dacron so treated is 19.

EXAMPLE 9 Examples 3 and 4 are repeated following the modifications ofExample 8, and the resultant Dacron swatches have brightness values of 7and 9, respectively.

EXAMPLE 10 Employing compound 3 of Example in the procedure of Example8, there results a brightness reading on the Dacron of 11.

Examples 8 through demonstrate that even at the minuscule amounts usedin these examples, there is a significant difference in brighteningamong the brighteners used and brightener A is again far superior.

EXAMPLE 11 Example 8 is again repeated except that in place of dimethylformarnide, the brightener is prepared in solution in hot methylCellosolve (ethylene glycol monomethyl ether). The results aresubstantially the same as those obtained in Example 8.

EXAMPLE 12 Example 8 is again repeated except that 300 ml. of hotethanol is used as the solvent in place of the dimethyl formamide and 6ml. aliquot of this solution is added to the laundering bath. Similarresults are obtained as in Example 8.

As pointed out above, mixed fiber batches are preferably brightened witha combination brightener, i.e., cellulosic brightener plus brightener A,and this is demonstrated in the following examples.

EXAMPLE 13 The procedure of Example 8 is repeated except that the amountof brightener A used is 0.00008 g. (0.02% by weight based on the weightof the detergent), and there is additionally added to the bath 0.0008 g.(0.2% by weight based on the weight of the detergent) of a cellulosicbrightener of structure X above. The Dacron swatch is found to have abrightness of 9 and the cellulose sw atch a brightness of about 100.

EXAMPLE 14 Example 13 is repeated except that brightener A is replacedby an equal weight of the brightener of Example 3. The Dacron swatchtreated in this manner has a brightness of 4, and the cellulose abrightness of about 100. The above two examples demonstrate theexcellent brightening of the cellulose by the cellulosic brightener aswell as the far superior brightening of the Dacron where brightener A isincluded in the bath vis-a-vis the Dacron brightening achieved with thecommercial brightener.

EXAMPLE 15 Example 13 is repeated replacing brightener A by an equalweight of brightener compound (1) of Example 5. The brightness of theDacron is improved slightly over that produced in Example 14 but theproduct is still much inferior to the brightened Dacron of Example 13..As in Examples 13 and 14, the cellulosic material has a bri htnessvalue of about 100.

EXAMPLE 16 Example 13 is once more repeated except that the detergentused contains in place of the :anionic surfactant component, sodiumdodecyl benzene sulfonate, an equal weight of nonyl phenoxynonaethyleneoxy ethanol. The brightness reading on the Dacron so treatedis 10. Replacing brightener A with the commercial brightener of Example3 produces a brightness on the Dacron of 5.

EXAMPLE 17 The procedure of Example 13 is again repeated except thatbrightener A is employed at a concentration of 0.05%. The Dacron swatchtreated in this manner is found to have a brightness of 17 and thecellulose swatch a brightness, again, of about 100. At thisconcentration, replacing brightener A with an equal weight of the brightener of Example 3, there results a brightening of a Dacron swatch to theextent of a brightness value of about 8.

EXAMPLE 18 The general procedure of Example 13 is again once morerepeated but the bath employed is one of 200 ml. in volume (i.e., aliquor to total cloth ratio of 40:1 instead of 20:1 as in Example '13).The Dacron swatch which results from this treatment has a brightnessvalue of 8.

EXAMPLE 19 Example 2 is repeated except that in the detergent formulathe sodium dodecyl benzene sulfonate is replaced by sodium decyl benzenesulfonate. Comparable results are obtained.

EXAMPLE 20 Example 2 is once more repeated in each of the followingexamples except that in each instance a different anionic detergent isemployed in the indicated amounts in place of the sodium dodecyl benzenesulfonate of Example 2:

(A) 15% of cyclohexyl ammonium dodecyl benzene sulfonate (B) 10%ammonium diisobutyl benzene sulfonate (C) 12% sodium octadecyl benzenesulfonate (D) 15% sodium diisobutyl naphthalene sulfonate (E) 15% sodiumkeryl benzene sulfonate Substantially the same results are obtained asin Example 2. In the above examples A through E the difierence betweenthe amount used and 15% is made up by adding that difference as apercent increase in the amount of sodium sulfonate in the detergentformulation.

EXAMPLE 21 Example 2 is again repeated except that the detergentemployed comprises the following ingredients in the ratio of theindicated parts:

Parts Surfactant (anionic phosphate ester described in Example 74 of US.Pat. 3,122,508) 10 Tetrapotassium pyrophosphate 25 Sodium oleate 7.2Sodium metasilicate 3 Sodium xylene sulfonate 5 Carboxy methyl cellulose0.5 Potassium hydroxide 2.5

Excellent brightness of the Dacron is obtained.

In the foregoing examples the brighteners are added to the detergentbath as a separate ingredient apart from the surfactant composition. Inthe following examples the brighteners employed are incorporated firstinto the detergent formulation and then the latter is added to the 100ml. of Water to conduct the tests in the brightening of the variousswatches immersed therein.

EXAMPLE 22 One part of brightener A is added to ten parts of the liquidnon-ionic surface active material described in Example 2. The mixture isheated to 130 C. whereby this solution of the brightener is obtained. Atthis temperature the solution is then added to a hot (100 C.) slurry ofan aqueous sodium dodecyl benzene sulfonate slurry containing about 75%active sulfonate and the balance water. This mixture is then thoroughlystirred to obtain uniform distribution of the brightener solution in thesulfonate slurry and the entire mixture is thereafter dried on a hotrotating drum. The amount of brightener solution used is adjusted sothat in the finalproduct there is present 0.4% by weight of brightener.This brightener sulfonate combination is then employed in place of the15% by weight of sodium dodecyl benzene sulfonate used in Example 2 andin combination with the remaining additives set out as being present inthe commercial detergent formulation recited in Example 2. In the finaldetergent formulation there is present about 0.06% by weight ofbrightener A based on the weight of the total ingredients of thedetergent composition. The general procedure of Example 2 is thencarried out to effect the brightening of the Dacron as described in thatexample. The brightness reading of the final dry Dacron swatch is 38.Repeating this procedure except that the commercial brightener ofExample 3 is used in place of brightener A results in the Dacron swatchhaving a brightness of only 9.

While brightener A of the present invention is most outstanding whenemployed in the manner described in the aforementioned examples, it mayalso be used, however, in combination with polymers and particularlypolyesters of the Dacron type in a melt incorporation technique. Ingeneral, to incorporate brightener A in polyethylene terephthalate, thelatter is melted under vacuum at 250 C. with about 0.01% of brightener Aand the melt then fashioned into any conventional form desired, such asfilms, fibers, or molded into any suitable shape. The resultant productsexhibit not only outstanding brightness but it is also found that thebrightener is remarkably stable to ambient influences. As evidenced bythe fact that after six months exposure outdoors, less than 15% of thefluorescence (brightness) is lost.

In Example 1 above there has been set forth a specific and detailedprocedure for producing the brightener A of this invention. It has alsobeen found that this compound may be produced by a somewhat modifiedprocess which is completely unforseen, particularly with regard to theoutstanding yields which are obtained. By this modification it ispossible to obtain the amino azo intermediate (the product used in theoxidation step to produce the final triazole) in most quantitativeyields. This modification follows the general procedure of Example 1except that in place of the 2-naphthylamine coupling component there isemployed an equivalent weight (i.e. 0.796 mol) ofl-sulfo-Z-naphthylamine and no glacial acetic acid is necessary sincethe coupler is soluble in water. After an aqueous solution of thecoupler has been slowly added to the diazonium compound, the pH of themixture is adjusted to about 7.5 with soda ash, the mixture then heatedto 45 C. and thereafter stirred for four hours. The product is isolatedas in Example 1 and oxidized to the triazole similar as in that example.Any unreacted azoamino compound may be destroyed by acidifying andwarming the material prior to isolation and recovery in the mannerdescribed in Example 1. This modified form of the process for producingbrightener A not only gives rise to exceptional yields of very pureproduct but furthermore avoids the use of 2-naphthylamine as a coupler,-Which may be objectionable.

EXAMPLE 23 Example 22 is repeated except that the 10 parts nonionicsurface active material used to prepare the initial brightener solutionis replaced by the following:

(A) 10 parts of octyl phenoxy dodeca ethylene oxy ethanol,

(B) 20 parts of nonyl phenoxy nona ethylene oxy ethanol,

(H) 10 parts of a tridecyl alcohol and 6 mols of ethylene oxidecondensate,

(I) 20 parts of a dodecyl amine and 20 moles of ethylene oxidecondensate,

(I) 15 parts of an isobutyl benzene sulfonamide and 30 mols of ethyleneoxide condensate.

The results in each instance are comparable to Example 22.

EXAMPLE 24 (A]) Example 2 is repeated 10 times except that in each casethe 20 cc. of nonyl phenoxy nona ethylene oxy ethanol of that example isreplaced by an equal weight of the surface active non-ionic compounds inExample 23 (A-I).

EXAMPLE 25 The general technique of Example 22 is followed to prepare abrightener A-detergent formulation based on the detergent described inExample 16. A 10% solution of the brightener in the non-ionic surfaceactive compound is first prepared and this is blended with a portion ofthe remaining ingredients to yield a paste containing about 1%brightener. This paste is then further blended with the remainingingredients on a ribbon blender to yield the final compositioncontaining about 0.04% brightener A. In this example the cellulosicbrightener is omitted. If the latter is desired, it may be addedseparately and blended with the paste or in the final mixing step usingany desirable concentration from about 0.05% to about 0.5%.

EXAMPLE 26 Example 13 is repeated several times replacing in eachinstance the cellulosic brightener X by the following:

(A) cellulosic brightener I, (B) cellulosic brightener III, (C)cellulosic brightener IV, (D) cellulosic brightener V, (E) cellulosicbrightener VI, (F) cellulosic brightener VIII.

The results are comparable to Example 13.

EXAMPLE 27 Example 22 is repeated except that there is additionallyadded to the hot slurry of sodium dodecyl benzene sulfonate sufficientof cellulosic brightene'r X to give a final concentration in thedetergent of 0.3%

@ Q-Qn dissolved in (b) a liquid non-ionic surfactant, the amount of (b)being to 500 times by weight the amount of (a) which is present in anamount of about 0.0050.5% based on the weight of the actual composition.

2. The brightener composition of claim 1 wherein said liquid non-ionicsurfactant (b) is a condensation roduct of an alkyl phenol containingfrom about to 35 carbon atoms and from 5 to about moles of ethyleneoxide per mole of said phenol.

3. The brightener composition of claim 1 wherein said liquid non-ionicsurfactant (b) is a condensation product of an alcohol of about 6 to 30carbon atoms and from 5 to about 30 moles of ethylene oxide per mole ofsaid alcohol.

4. The brightener composition of claim 1 wherein said compositionadditionally contains (0) a stilbene-cyanuric brightener in a ratio of(c) to (a) of from about 1:1 to about 100:1.

5. The brightener composition of claim 4 wherein the ratio of (c) to (a)is from 10:1 to 30: 1.

6. The brightener composition of claim 4 wherein said liquid non-ionicsurfactant (b) is a condensation product of an alkyl phenol containingfrom about 10 to carbon atoms and from 5 to about 30 moles of ethyleneoxide per mole of said phenol.

7. The brightener composition of claim 4 wherein said liquid non-ionicsurfactant (b) is a condensation product of an alcohol of about 6 to 30carbon atoms and from 5 to about 30 moles of ethylene oxide per mole ofsaid alcohol.

8. A detergent composition consisting essentially of (1) a nonionic oranionic detergent and (2) a brightener composition consistingessentially of (a) a compound of the formula dissolved in (b) a liquidnon-ionic surfactant, the amount of (b) being 5 to 500 times by weightthe amount of (a), said brightener composition being present in such anamount that said compound (a) is present in an amount of 0.005% to about0.5% by weight based on the total composition.

9,. The detergent composition of claim 8 wherein said liquid non-ionicsurfactant (b) is a condensation product of an alkyl phenol containingfrom about 10 to 35 carbon atoms and from 5 to about 30 moles ofethylene oxide per mole of said phenol.

The detergent composition of claim 8 wherein said liquid non-ionicsurfactant (b) is a condensation product of an alcohol of about 6 to 30carbon atoms and from 5 to about 30 moles of ethylene oxide per mole ofsaid alcohol.

11. The detergent composition of claim 8 wherein said compositionadditionally contains in said brightener composition (c) astilbene-cyanuric brightener in a ratio of (c) to (a) of from about 1:1to about :1.

12. The detergent composition of claim 11 wherein the ratio of (c) to(a) is from 10:1 to about 30:1.

13. The detergent composition of claim 11 wherein said liquid non-ionicsurfactant (b) is a condensation product of an alkyl phenol containingfrom about 10 to 35 carbon atoms and from 5 to about 30 moles ofethylene oxide per mole of said phenol.

14. The detergent composition of claim 11 wherein said liquid non-ionicsurfactant (b) is a condensation product of an alcohol of about 6 to 30carbon atoms and from 5 to about 30 moles of ethylene oxide per mole ofsaid alcohol.

References Cited UNITED STATES PATENTS 2,213,477 9/1940 Steindorfi" etal. 25289 2,703,801 3/1955 Rottschaefer et al. 260240B 2,713,046 7/1955Williams et a1 260240B 2,793,192 5/1957 LeaW/itt 252-890B 2,840,5576/1958 Williams et al 260240B 3,288,786 11/1966 Strobel et a1. 252301.2

FOREIGN PATENTS 12,834 3/1962 Japan.

LEON D. ROSDOL, Primary Examiner W. E. SCHULZ, Assistant Examiner US.Cl. X.R.

